Fluorine-containing lubricant



Patented Feb. 3, 1953 UNITED STATES PATENT OFFICE FLUORINE-GONTAINING LUBRICANT Harry L. Coonradt, Woodbury, BartonW. Rope, ll iullica Hill, and Alexander N. Sachanen, Woodbury, N. J assignors to Snoopy-Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application August 10, 1950, Serial No. 178,747

3 Claims.

oi desirable properties, with emphasis being dirooted to high viscosity index (V. I.) and stability under rigorous operating conditions. While the parafiinic-type lubricants, typified by Pennsylvam'a oils, have relatively high viscosity indices, they have not been able to satisfy the demands of present day operations in regard to chemical and thermal stability. Naphthenicand aromatictype lubricants, illustrated by Mid-Continent and Coastal oils, have undesirably low viscosity indices. Such disadvantageous characteristics of conventional oils have been countered 0r eliminated, in some instances, by incorporating with the oils one or more adjuvants, particularly V. I. improvers, oxidation inhibitors or stabilizers, and the like. In many cases, however, the improvement realized has been insuiiicient. This is illustrated by heavy duty motor oils, extreme pressure lubricants, hydraulic oils, etc. A further illus tration is that of lubricating oils for high-pressure oxygen compressors. Conventional petroleum oils and synthetic organic lubricating oils burn rapidly on operation of such compressors and frequently form explosive mixtures with oxygen. There remains today, therefore, a de-- mand for lubricants of excellent V. I. and stability.

Among the materials hitherto proposed as possible lubricants, in View of their exceptional chemical and thermal stability, are the fluorocarbons, Facb, wherein a and b are integers. Unfortunately however, it has been found that fiuorocarbons are uniformly characterized by low V. I. and high pour point values. For example, a perfiuorinated octadecane has a calculated V. I. of -430. Fluorine-containing organic com pounds have also been proposed as lubricants. Here again, success has been rather limited. By way of illustration, fluorine-containing compounds obtained by decomposing fluorine-containing polymers of tetrafluoroethylene and chlorotrifluoroethylene, have proven to be semi-solids or oily materials having poor viscosity indices and/or excessively high pour points. Other fluorine-containing compounds have been noted for their exceptional stability, and. among such 2 compounds are the polyfiuorocyclobutanes described by Barrick in U. S. Letters Patent Nos. 2,4 4,123 and 2,462,345. The polyfiuorooyclobutanes described therein, however, are not suitable for use as lubricants; some are solids, others are of low viscosity and suitable for use as solvents and reaction media.

Surprisingly, it has now been found that a certain, well-defined group of polyfiuorocyclobutanes are excellent lubricants, having desirably high V. I., chemical and thermal stability, and satisfactory pour characteristics. The polyfiuorocyclobutanes contemplated herein are represented by the following general Formula I:

wherein n is an integer from about 11 to about 19. and is preferably from about 13 to about 1'7.

Catalytic oxidation stability tests demonstrate the materials contemplated herein-to bev superior to uninhibited Pennsylvania type mineral oils. The characteristics of the new compositions are such as to make them outstanding synthetic lubricants, for use alone or blended withother lubricants.

The polyfiuorocyclobutanes of this invention are prepared by reaction of tetrafiuoroethylene with a straightt chain, alpha hydrocarbon olefin having from about fourteen to about twenty-two carbon atoms per molecule. In accordance with the invention, the most desirable synthetic oils are those produced from straight chain, alpha mono-olefins having from about sixteen to about twenty carbon atoms per molecule. Typical 01efins are: n-tetradecene-l; n-hexadecene-l; noctadecene-l; n-eicosene-l; and n-docosene-l.

The sate of purity of the straight-chain, alpha mono-olefin reactant from which the polyfiuorocyclobutanes are derived, does not appear to be especially critical. It is desirable, however, to have a starting material which contains as large a percentage of the above-described alpha olefins as possible. It is permissible to have present lesser amounts of. other olefins and of other hydrocarbon materials. In general, the olefinic charge preferably should contain less than about twenty per cent by weight of unsaturated hydrocarbons otherthan straight chain, alpha monoolefins having from about fourteen to about twenty-two carbon atoms per molecule. However, since paraffins are not invol'vedin the reaction. with tetrafiuoroethylene, the alpha-olefin...

3 containing charge can contain a much as fifty per cent by weight of paraffinic hydrocarbons with the balance the specified normal, alpha mono-olefins. In many instances, in commercial operation, it will be found desirable to use technical grades of such olefins as n-tetradecene-l, n-hexadecene-l and the like. Mixed olefinic materials derived from the thermal cracking of wax or from the Fischer-Tropsch process constitute satisfactory charging stock. In this connection, it should be noted that it is suspected that substantially straight chain l-olefins having between about fourteen and about twenty-two carbon atoms per molecule, that is, l-olefins in which the length of the side chain or chains is short relative to the length of the main carbon chain,

are also suitable, although less preferred olefin reactants for the purpose of the present invention. However, in view of the fact that such olefinsare unavailable, no test data can be adduced to confirm this suspicion.

The polyfluorocyclobutanes are prepared by heating, under autogenous pressure, the monoolefin and tetrafluoroethylene reactants. Temperature of reaction can be varied over a wide range, as from about 200 F. to about 800 F. It will be understood, of course, that excessively high temperatures at which the reactants and/or products decompose, are to be avoided. In general, temperatures within the range of 409 F. to 600 F. are preferred. As indicated, the pressure at which reaction is conducted depends upon the natureof the reactants, equipment and other reaction conditions such as temperature. Generally, high pressures favor the reaction. Satisfactory operations have been attended by autogenous pressures from about 400 to 609 pounds per square inch. Reaction is generally carried out in a closed system. However, the reactants can be passed continuously through a hot reaction tube.

Reaction of the aforesaid olefins and tetra fiuoroethylene is quite rapid as indicated by a decrease in pressure When the reactants are brought together at a suitable temperature. Thus, the reaction time can be as low as several minutes, or can be extended, depending upon the nature of the reactants, temperature, etc. Reaction periods between about one-half hour and about two hours have proven advantageous.

The proportions of the alpha mono-olefin and of the tetrafluoroethylene reactants are also susceptible of variation, although the principle reaction involves the combination of equimolar quantities of the two reactants. One competing reaction is the polymerization of the monoolefin hydrocarbon reactant. Under the conditions of the reaction, and as shown by Seger and Sachanen in 2,500,166, thermal polymerization of normal, alpha monoolefins is of little consequence at temperatures below 500 F. unless such temperatures are maintained for an extremely long period of time, c. g., forty hours. Moreover, reaction of tetrafluoroethylene with the olefin is much more rapid than olefin polymerization. In the instant reaction, therefore, polymerization of the normal, alpha monoolefin reactant is not a serious factor. Another side reaction is the dimerization of tetrafluoroethylene. Inasmuch as this competing reaction consumes the reactant' which is generally more expensive, it' is usually advantageous to use an excess of normal, monoolefin reactant.

In regard to selecting a proper proportion of reactants and operating technique, to obtain the V effecting reaction of the foregoing reactants. As

products.

shown in the typical examples hereinbelow, unstabilized anduninhibited reactants have been reacted successfully to provide the desired products. It will be understood, of course, that a polymerization inhibitor can be incorporated into the reaction mixture, if desired, particularly to inhibit polymerization of tetrafluoroethylene, although our investigations indicate that an inhibitor is not essential.

In order to illustrate the principles of this invention several typical, and non-limiting, preparations are described in the following examples. These preparations were carried out in a rocking-type bomb (American Instrument Co.) The reactants were charged to the bomb, which was then heated to the desired temperature for the desired time interval. Thereafter, the bomb was cooled, and discharged. The contents of the bomb were vacuum distilled to separate thereaction product into several fractions, namely, unreacted materials, desired product and by- It should be noted that the reaction times, given in the examples, represent the time interval during which the bomb was maintained at the desired temperature, and do not include the time intervals necessary to heat the bomb and its contents to the desired temperature, and do not include the time intervals necessary to cool the bomb after heat to the bomb has been discontinued.

EXAMPLE I Equimolar proportions of n-octadecene-l, eighty-five parts by weight, and of tetrafluoroethylene, thirty-three parts by weight, were char ed to a bomb, and heated at 53D-54i) F. under autogenous pressure (maximum, 400 pounds per square inch) for eight hours. .One hundred-and-two parts (weight) of liquid prod not were obtained. The liquid product was distilled to a maximum temperature of 272 F. at 1 min. of mercury. In addition to recovered n-octadecened, 29.3 parts (weight) of addition prodnot were obtained. The addition product boils at 127.5-133.5 C. (26l.572.3 F.) at 1 mm. of mercury, and has a refractive index 15 of M1212. Analysis revealed a carbon content of 67.4 per cent and a fluorine content of 22.1, which compares well with 68.1 per cent carbon and 21.6 per cent fluorine, respectively, for CzoI-IacF-r. The product can be represented as Infrared spectrographic analysis of the product disclosed no absorption in the region 5.35.9 microns, which is characteristic of fluorocarbon olefins.

EXAlvIPL-E II A. bomb of the aforesaid character was charged assesseof n-octadecene-"1- and 1.52 molar remiering- (152 parts by weighty of tetr'afluoroethyleiia- The mixture was heated at 545 556 F. for two hoursand forty minutes rinse-reuse ribus prss:

sure (maximum 560 pounds per square inch Liquid product recovered from the bomb corriprised 426.6 parts (Weight). T was distilled to amaximum tenperatiire 0 5 161 C. at 1 mm. of Hg. Additionprodilct redifiiered comprised 1583 parts (Weight) this 2. 13011 ingpoint of 155 160 C. ar -1' nimtof'Hg-l This product is predominantly C20H'36F4.

There also was obtained 03.3p'arts (weight) or product having a boiling poiht'above 1'61 C. at 1 mm. of Hg. This'productc'oiitains 7 genes cut of fluorine The nature'of misproduct'na not yet been definitelyes'tablished; It-n'iost probably is a complex mixture" containing an addition product of tetrafiuoroethylene a'ndan: unsaturated ther n'ial polymer of n octadecene-l.

The physical propertie'scf the p'rod-uct CztHzsFr arelisted below:

Ihe physical properties, particularly viscosity, of the polyfluorocyclobutane, indicate that it falls close to the proposed classification of SAE 5 lubricants. The polyfluorocyclobutane, therefore, is suitable for use in engine lubrication, transformer oils, etc.

EXAMPLE III A stainless steel bomb with a void of approxt mately one liter was charged with 295.8 grams (1.5 mol) of n-tetradecene-l and 155 grams (1.55 mols) of tetrafluoroeth'ylene. The mixture was heated at about 550 F. underau'togenous pressure (maximum, 400 pounds per square inch) with shaking for three hours. The bombwascooled and gaseous material vented. Liquidproductre covered comprised 377 grams. When the latter was distilled to a maximum' temperature of 253 F. at 4 mm. of Hg, there Wasobtained 162.5 grams of addition product. Properties of the addition product include:

Kinematic viscosity 100 F -1 4.21 Kinematic viscosity 210 F 1.46 V. I. (calculated) 111 Boiling point, F. 4 mmsL I-Ig-11 236-253 Boiling point, 760 mms. Hg

(calc.) 523532 Refractive index, 11 -1 1.4120 Fluorine, weight per cent 25.5

is suitable for use as a transformer oil and for special lubrication where a light oil is required.

EXAMPLE IV That the lubricants of this invention have cxliquid product 6 c'lle'rit stability "is shj n' oxidation est; ,wmcn ear h s toward ea aly'uc xms Thetestresults'are shown below 'in Table-I. V

The test oil,-20 or 25 ccsi, i's placedin a 200 1125 mm's. test tube with 15. 6" square inches of sandblasted iron wire, 0178" square manor polished copper-wire, 0 .87 square'inch' of -polished alumi mm wire} and 0;-1 67 s"q iiare1 inclr ofpolished'leadplate. Dry air is pa'ssed' through the sampleof oil at a-rate" o' f 1'0liters p'er hour. The test tube is heated at 260 F. for "to-hour's in-an aluminum block bath; The results-reportetlatthe end' or the test are: neutralization number (N. .N.)';-'lper cent viscosity increase at 210 F.; sludge and lacquer; lead weight loss (ii'r milligramsl; and appearance" of copper. The oil* is compared with a reference oil of similar viscosityand is'rated'on the basis of viscosity increase, N. N. increase, sludge and lead weight loss. A maximum of three demerits is assigned to each factor rated. The sum of the demerits for an oil is called the stability number and ranges from 0 to 12. The reference mineral oils, 'solvent refined Pennsyl vania oils; have stability numbersofdto'f.

Also shown in Table I is at'e'st' with the poly'-- iiuorocyclobutane obtained from n-octadecene-l (Example II) having incorporated therewith a small amount of an outstanding inhibitor comprising an oil-soluble, .p'no pnsrw containing. reactionpro" phorus penta'sulfide', tail in Patent No; j-2,4'1 1. v e, that us dcontained' aboutlfi per cent snare'a'cutnrroauctassessmen s of'rnlneral oil.

a catalytic It-Will be noted that s tests on the Siamese lubricant were rnadef oriiBDfrril. samples in con: trait s h 51 21? Q?" r fl i c he wer a d mea 'w i m I presentwere maintained ;at theregularitest le l' h s ee ie-.srflhfic: @l l W r tu vfmo ie severe vthan r arrn'a l and theife t w of th'esynthetic oil is rated cease Table? oirrnrrronsrrsimrr or cits It is-appa'rent' from the results shown in Table I that the polyfluorbcyclobutane"lubricant is sub stantially more stable in "all respects than the referenceoil. Particularly; the increasesinvis cosity and in N. Nxvalues are mucli lessthan the corresponding values of the reference oil; In

addition; the synthetic-lubri'cant responds well to the -inhibitor, pa'rticularly asevidencedby the further improvementin reducing -the leadloss.

EXAMPLE V The polyfluorocyclobutane derived from tetrafluoroethylene and n-octadecene-l, products from Examples I and 11 combined, is also excellent as an extreme pressure lubricant. This is.

"tabilityof "oils inhibitor" or" demonstrated by results obtained in the Falex wear test. This test is described in the minutes of the SAE Society, September 29-October 1, 1937, in a publication of Crowley and Faville. The test involves rotation of a small steel pin between two steel V blocks in a bath of the lubricant, under increasing pressure upon the pin. The most significant result of the test is the pressure atseizure. The pressure, in pounds per square inch, refers to the hydraulic pressure of the pump loading specimens. Temperature is also reported for its gives some indication of the effectiveness of the lubricant, since all tests start at 100 F. and the rise in temperature is related to friction.

Shown also in Table II for comparative purposes is a typical mineral oil, and a typical fortifled lubricant comprising mineral oil and oil addition agents.

Table II Lubricant f 2 SAE EEO-straight mineral oil 240 121 SAE +1% A l 240 206 Addition Product, Example V l. 450 l28 I Additive A described in Example IV.

The test results in Table II reveal that the polyfiuoroeyclobutane derived from n-octadecene-l is superior to conventional lubricants in withstanding extreme pressures.

As will be evident from the data presented above in Tables I and II, the condensation products of this invention are highly desirable lubricants per se. They are also of considerable value as blending agents for other lubricating oils. In view of the inherent stability of the synthetic oils, they impart stability to the oils with which they are blended. So also, they impart desirable viscosity index (V. I.) to the oils in combination therewith, for as indicated above, they have advantageous viscosity index properties. In short, the synthetic oils find utility in upgrading other lubricants. Typical oils with which the synthetic oils may be blended are mineral oils such as are normally used in internal combustion and turbine engines. When so blended, the synthetic oils may comprise the major proportion of the final blended oil, or may even comprise a minor proportion thereof. For example, although used only in the amounts of the order of 1-10 per cent, the synthetic oils improve the stability of mineral oils, such as SAE 10 and Pennsylvania type oils. Thus, the lubricants of this invention are in sharp contrast with perfiuorinated hydrocarbons which are immiscible with mineral oils.

One or more of the individual properties of the synthetic lubricants of this invention may be further improved by incorporating therewith a small, but effective amount, of an addition agent such as an antioxidant, a detergent, an extreme pressure agent, a foam suppressor, a viscosity index (V. I.) improver, etc. Antioxidants are wellknown in the art, and are generally characterized by phosphorus, sulfur, nitrogen, etc. content; representative of such materials is an oil-soluble, phosphorusand sulfur-containing reaction 8 product of pinene and phosphorus pentasulfide. Typical detergents which may be so used are metal salts of alkyl-substituted aromatic sulfonic or carboxylic acids, as illustrated by diwax benzene barium sulfonate and barium phenate, barium salt of a wax-substituted phenol carboxylic acid. Extreme pressure agents are well known; illustrating such materials are numerous chlorine and/or sulfur containing compositions, one such material being a chlornaphtha Xan- .-thate. Silicones, such as dimethyl silicone, may

be used to illustrate foam suppressing compositions. Viscosity index improving agents which may be used are typified by polypropylenes, polyisobutylenes, polyacrylate esters, and the like.

Contemplated also as Within the scope of this invention is a method of lubricating relatively moving surfaces by maintaining therebetween a film consisting of any of the aforesaid oils.

It is to be understood that the foregoing description and representative examples are nonlimiting and serve to illustrate the invention, which is to be broadly construed in the light of the language of the appended claims.

A related group of synthetic lubricants of excellent quality is described by one of the applicants, A. N. Sachanen, in related application Serial No. 178,749 filed concurrently herewith, now Patent No. 2,582,283, issued January 15, 1952. The lubricants of the latter application are polyfluorodicyclobutanes represented by general Formula II.

wherein n is an integer from about ten to about eighteen, and is preferably from about twelve to about sixteen.

We claim:

wherein n is an integer from about eleven to about nineteen.

Ill H2CC{CH2)11CH3 HARRY L. COONRADT. BARTON W. ROPE. ALEXANDER N. SASHANEN.

REFERENCES CITED The following references are of record in the I) file of this patent:

UNITED STATES PATENTS Number Name Date 2,449,631 Zimmer Sept. 21, 1948 2,462,345 Barriok Feb. 22, 1949 

